Anion exchange polymers, methods for making and materials prepared therefrom

ABSTRACT

A novel anion exchange polymer is provided. A method of making the anion exchange polymer includes reacting a tertiary amine, an acid inhibitor and a polyepoxide to form a quaternary ammonium monomer and polymerizing the quaternary ammonium monomer in the presence of a catalyst. The exchange polymer is prepared without using alkyl halides and can be used to make improved ion exchange materials that are chemically resistant and non-fouling.

FIELD OF THE INVENTION

This invention relates to ion exchange polymers and more particularly,to anion exchange polymers and materials.

BACKGROUND OF THE INVENTION

Ion exchange materials are commonly employed to treat and removeionizable components from fluids for a variety of applications.Flow-through beds or flow-through devices for fluid treatment may employexchange material or components in the form of grains, fabrics ormembranes. The ion exchange functionality operates to transport one typeof ion across the material in an electric field, while substantially oreffectively blocking most ions of the opposite polarity. Anion exchangepolymers and materials carry cationic groups, which repel cations andare selective to anions.

Anion exchange polymers may be prepared from tertiary amines, which arequaternized to provide anionic functionality. The quaternary ammoniumcompounds are crosslinked and polymerized to form anion exchangepolymers. Typical methods for making anion exchange polymers require theuse of alkyl halides for quaternizing the anion exchange polymer.

Alkyl halides are expensive and hazardous to use. It would be desirableto prepare improved anion exchange polymers having superior propertieswithout using alkyl halides.

SUMMARY OF THE INVENTION

In one embodiment, an anion exchange polymer has the formula:

wherein R is —[CH₂—CH(OH)]₂—W; R₁ is hydrogen or a C₁-C₁₂ alkyl group; ais from about 0 to about 0.75, b and c are each independently, fromabout 0.25 to about 1.0; Z is oxygen or N—R₃; R₂ is —[CH₂]_(n)—; R₃ ishydrogen or —[CH₂]_(m)—CH₃; R₄ and R₅ are each, independently,—[CH₂]_(m)—CH₃; X is selected from the group consisting of Cl, Br, I andacetate; W is a bridging group or atom; m is an integer from 0 to 20; nis an integer from 1 to 20; and Y is selected from the group consistingof

wherein R₆, R₇ and R₈ are each, independently, selected from the groupconsisting of hydrogen, —[CH₂]_(q)—CH₃ and —CH(CH₃)₂; R₉ is —[CH₂]_(p);p is a number from 3 to 6 and q is a number from 0 to 3.

In another embodiment, a method for making an anion exchange polymercomprises reacting a tertiary amine, an acid inhibitor and a polyepoxideto form a quaternary ammonium monomer and polymerizing the quaternaryammonium monomer in the presence of a catalyst.

In another embodiment, an ion exchange material comprises an anionexchange polymer having the formula:

wherein R is —[CH₂—CH(OH)]₂—W; R₁ is hydrogen or a C₁-C₁₂ alkyl group; ais from about 0 to about 0.75, b and c are each independently, fromabout 0.25 to about 1.0; Z is oxygen or N—R₃; R₂ is —[CH₂]_(n)—; R₃ ishydrogen or —[CH₂]_(m)—CH₃; R₄ and R₅ are each, independently,—[CH₂]_(m)—CH₃; X is selected from the group consisting of Cl, Br, I andacetate; W is a bridging group or atom; m is an integer from 0 to 20; nis an integer from 1 to 20; and Y is selected from the group consistingof

wherein R₆, R₇ and R₈ are each, independently, selected from the groupconsisting of hydrogen, —[CH₂]_(q)—CH₃ and —CH(CH₃)₂; R₉ is —[CH₂]_(p);p is a number from 3 to 6 and q is a number from 0 to 3.

In another embodiment, a method for making an ion exchange materialcomprises reacting a tertiary amine, an acid inhibitor and a polyepoxideto form a quaternary ammonium monomer and polymerizing the quaternaryammonium monomer in the presence of a catalyst.

The various embodiments provide improved anion exchange polymers,methods for preparing the anion exchange polymers without using alkylhalides and for materials that are chemically resistant and non-fouling.

DETAILED DESCRIPTION OF THE INVENTION

The singular forms “a,” “an” and “the” include plural referents unlessthe context clearly dictates otherwise. The endpoints of all rangesreciting the same characteristic are independently combinable andinclusive of the recited endpoint. All references are incorporatedherein by reference.

The modifier “about” used in connection with a quantity is inclusive ofthe stated value and has the meaning dictated by the context (e.g.,includes the tolerance ranges associated with measurement of theparticular quantity).

“Optional” or “optionally” means that the subsequently described eventor circumstance may or may not occur, or that the subsequentlyidentified material may or may not be present, and that the descriptionincludes instances where the event or circumstance occurs or where thematerial is present, and instances where the event or circumstance doesnot occur or the material is not present.

The anion exchange polymer contains cationic groups. In one embodiment,an anion exchange polymer has the formula:

wherein R is —[CH₂—CH(OH)]₂—W; R₁ is hydrogen or a C₁-C₁₂ alkyl group; ais from about 0 to about 0.75, b and c are each independently, fromabout 0.25 to about 1.0; Z is oxygen or N—R₃; R₂ is —[CH₂]_(n)—; R₃ ishydrogen or —[CH₂]_(m)—CH₃; R₄ and R₅ are each, independently,—[CH₂]_(m)—CH₃; X is selected from the group consisting of Cl, Br, I andacetate; W is a bridging group or atom; m is an integer from 0 to 20; nis an integer from 1 to 20; and Y is selected from the group consistingof

wherein R₆, R₇ and R₈ are each, independently, selected from the groupconsisting of hydrogen, —[CH₂]_(q)—CH₃ and —CH(CH₃)₂; R₉ is —[CH₂]_(p);p is a number from 3 to 6 and q is a number from 0 to 3.

In one embodiment, R₁ is a C₁-C₆ alkyl group. In another embodiment, R₁is methyl, ethyl, propyl, butyl or isobutyl.

In one embodiment, a is from about 0.25 to about 0.50. In anotherembodiment, b is from about 0.50 to about 0.75. In another embodiment, cis from about 0.50 to about 0.75.

In one embodiment, Z is ammonia, trimethylammonia or triethylammonia.

W is a bridging group or atom. In one embodiment, W is a hydrocarbongroup, an inorganic group or inorganic atom. In one embodiment, W is aC₁-C₃₀ alkyl group, C₁-C₃₀ alkyl ether group, C₆-C₃₀ aromatic group,C₆-C₃₀ aromatic ether group or a siloxane. In another embodiment, W is aC₁-C₆ alkyl group, C₁-C₆ alkyl ether group, a C₆-C₁₀ aromatic group or aC₆-C₁₀ aromatic ether group. In another embodiment, W is methyl, ethyl,propyl, butyl, isobutyl, phenyl, 1,2-cyclohexanedicarboxylate, bisphenolA, diethylene glycol, resorcinol, cyclohexanedimethanol,poly(dimethylsiloxane), 2,6-tolylene diisocyanate, 1,3-butadiene ordicyclopentadiene.

In one embodiment, m is an integer from 0 to 10, including from 0 to 5.In another embodiment, n is an integer from 1 to 10, including from 1 to5.

In another embodiment, a method for making an anion exchange polymercomprises reacting a tertiary amine, an acid inhibitor and a polyepoxideto form a quaternary ammonium monomer and polymerizing the quaternaryammonium monomer in the presence of a catalyst.

The tertiary amine may be an ethylenic tertiary amine. In oneembodiment, the ethylenic tertiary amine is selected from the groupconsisting of dimethylaminopropylmethacrylamide (DMAPMA),dimethylaminopropylacrylamide (DMAPAA), diethylaminopropylmethacrylamide(DEAPMA), dimethylaminoethylmethacrylate (DMAEMA) and mixtures thereof.In another embodiment, the ethylenic tertiary amine monomer is DMAPMA.

The polyepoxide may be any type of polyepoxide having at least twoepoxide groups. In one embodiment, the polyepoxide is a diglycidyl etheror a triglycidyl ether. Diglycidyl ethers include, but are not limitedto, diethylene glycol diglycidyl ether, diglycidyl1,2-cyclohexanedicarboxylate, N,N-diglycidyl-4-glycidyloxyaniline,bisphenol A diglycidyl ether, brominated bisphenol A diglycidyl ether,bisphenol F diglycidyl ether, 1,4-butanediol diglycidyl ether,1,4-butanediyl diglycidyl ether, 1,4-cyclohexanedimethanol diglycidylether, glycerol diglycidyl ether, resorcinol diglycidyl ether,bis[4-(glycidyloxy)phenyl]methane, bisphenol A propoxylate diglycidylether, dimer acid diglycidyl ester, ethylene glycol diglycidyl ether,brominated neopentyl glycol diglycidyl ether, diglycidylether-terminated poly(dimethylsiloxane), poly(ethylene glycol)diglycidyl ether, poly(propyleneglycol) diglycidyl ether,1,2,3-propanetriol glycidyl ether and 1,3-butanediol diglycidyl ether.Triglycidyl ethers include, but are not limited to,tris(2,3-epoxypropyl)isocyanurate, trimethylolpropane triglycidyl ether,tris(4-hydroxyphenyl)methane triglycidyl ether 2,6-tolylenediisocyanate, tris(4-hydroxyphenyl)methane triglycidyl ether, glycerolpropoxylate triglycidyl ether and trimethylolethane triglycidyl ether.

In another embodiment, the polyepoxide is a diepoxide. Diepoxidesinclude, but are not limited to, 1,3-butadiene-diepoxide, 1,3-butadienediepoxide, dicyclopentadiene dioxide, methylcis,cis-11,12;14,15-diepoxyeicosanoate.

The epoxide quaternizes the tertiary amine to form a quaternary ammoniummonomer. The quaternary ammonium monomer is also crosslinked by theepoxide to make the monomer water insoluble. Without crosslinking, thepolymers would dissolve in water and would be ineffective for use in ionexchange materials. In one embodiment, the monomer is highlycrosslinked. In another embodiment, the polymer is crosslinked in therange of from about 50 to about 100 percent. In another embodiment, thepolymer is fully crosslinked.

Polymerization of the quaternary ammonium monomer to form the anionexchange polymer can occur simultaneously with the reaction forquaternizing and crosslinking the tertiary amine. The reaction of thetertiary amine and polyepoxide and the polymerization reaction may becarried out by heating the reactants and monomers to a suitabletemperature and for a time sufficient for quaternizing and crosslinkingthe tertiary amine and for polymerizing the quaternary ammonium monomer.In one embodiment, the temperature range is from about 40° C. to about150° C. In another embodiment, the temperature range is from about 60°C. to about 110° C. and in another embodiment, the temperature range isfrom about 85° C. to about 100° C. In one embodiment, the reaction timeis from about 1 minute to about 2 hours. In another embodiment, thereaction time is from about 10 minutes to about 1 hour. In anotherembodiment, the reaction time is from about 20 minutes to about 45minutes.

The quaternization is conducted in the presence of an acid inhibitor,which controls the polyepoxide from self polymerization. The acidinhibitor prevents the polyepoxide from self polymerizing by quenchingthe reaction. The amount of quenching is controlled by the amount ofacid inhibitor used in the reaction. The acid inhibitor may be any typeof acid. In one embodiment, the acid inhibitor is a mineral acid. Inanother embodiment, the acid inhibitor includes, but is not limited to,hydrochloric acid, methane sulfonic acid, sulfuric acid or phosphoricacid. The acid inhibitor is added in any amount suitable for quenchingthe polyepoxide. In one embodiment, the acid inhibitor is present in anamount of from about 75 percent by mole weight to about 125 percent bymole weight, based on the mole weight of the tertiary amine. In anotherembodiment, the acid inhibitor is present in an amount of from about 75percent by mole weight to about 100 percent by mole weight, based on themole weight of the tertiary amine.

The anion exchange polymer may be synthesized using a wide ratio rangeof the tertiary amine to the polyepoxide. In one embodiment, the ratiois from about 0.3 to about 1.5 moles of the tertiary amine to eachequivalent mole of the polyepoxide. In another embodiment, the ratio isfrom about 0.5 to about 1.0 moles of the tertiary amine monomer perequivalent mole of the polyepoxide.

A catalyst is added to aid in polymerization. The catalysts may bespontaneously activated or activated by heat, electromagnetic radiation,electron beam radiation or by chemical promoters. The catalyst may beadded in any amount suitable for aiding in polymerization. In oneembodiment, the catalyst is in an amount of from about 0.1 to about 5.0percent by weight of the reaction mixture.

The catalyst may be any type of catalyst suitable for polymerizing thequaternary ammonium monomer. In one embodiment, the catalyst is aperoxide. The peroxide includes, but is not limited to, methyl ethylketone peroxide and dibenzoyl peroxide. In another embodiment, thecatalyst is a water soluble or oil soluble azo initiator. The azoinitiator includes, but is not limited to,2,2′-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride,2,2′-azobis(N,N′-dimethylene isobutyramidine)dihydrochloride,2,2′-azobis(2-methylpropionamidine)dihydrochloride,2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate,2,2′-azobis {2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl)propane],2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] and dimethyl2,2′-azobis(2-methylpropionate).

The term “chemical promoters” as used herein refers to a substance,which increases the rate of polymerization either by itself or incombination with another catalyst. For example, methyl ethyl ketoneperoxide can function as a catalyst itself, but its rate of initiationcan be greatly increase by small amounts of transition metal saltchemical promoters, such as, for example, cobalt naphthenate. Similarly,dibenzoyl peroxide can function as a catalyst itself, but its action beaccelerated by a dimethylaniline chemical promoter. The UV radiationpolymerization agents can become more efficient in the presence ofchemical promoters, which are photoinitiators or chemical compounds thatgenerate free radicals. Non-limiting examples of photoinitiatingchemical promoters include benzophenone, benzyl, antraquinone, eosin andmethylene blue.

In one embodiment, the components are combined in the presence of asolvent. Any solvent is suitable for use in this embodiment, so long asthe solvent is not itself polymerizable and the components are solublein it. Solvents suitable in this embodiment include, but are not limitedto, water, polyethylene glycols, dimethylsulfoxide, 2-pyrrolidone,N-methyl pyrrolidone and mixtures thereof.

The amount of solvent is added in any amount suitable for solubilizingthe components. In one embodiment, the amount of solvent is from about10 to about 90 percent by weight based on the total weight of thereaction mixture. In another embodiment, the amount of solvent is fromabout 20 to about 70 percent by weight based on the total weight of thereaction mixture. In another embodiment, the amount of solvent is fromabout 25 to about 50 percent by weight based on the total weight of thereaction mixture.

The components are combined and reacted in any conventional manner. Theorder of addition is not critical and the components may be added in anyorder.

An example of a reaction forming a quaternary ammonium monomer byreacting DMAPMA with a polyepoxide and hydrochloric acid (HCl) is shownbelow:

Additionally, other ethylenic monomers may be added to thepolymerization mixture to increase or decrease the ion exchange capacityof the resulting ion exchange polymer. Examples of ethylenic monomersthat lower the ion exchange capacity include, but are not limited to,methacrylamine, N-methylmethacrylamide, N-vinyl pyrrolidinone andN-vinyl caprolactam. Examples of ethylenic monomers that raise the ionexchange capacity include, but are not limited to, methacrylamidopropyltrimethylammonium chloride (MAPTAC) and trimethylammoniumethylmethacrylate chloride (TMAEMC).

These ethylenic monomers may be added to the reaction mixture with theother reactants and may be added in any order with the reactants. Theethylenic monomers may be added in any amount suitable for affecting theion exchange capacity of the ion exchange polymer. In one embodiment,the ethylenic monomer is added in an amount of from about 0 to about 50molar percent of the tertiary amine. In another embodiment, theethylenic monomer may be added in an amount of from about 10 to about 40molar percent of the tertiary amine. In another embodiment, theethylenic monomer may be added in an amount of from about 20 to about 40molar percent of the tertiary amine.

The anion exchange polymer may be used to form ion exchange materials.In one embodiment, an ion exchange material comprises an anion exchangepolymer having the formula:

wherein R is —[CH₂—CH(OH)]₂—W; R₁ is hydrogen or a C₁-C₁₂ alkyl group; ais from about 0 to about 0.75, b is and c are each independently, fromabout 0.25 to about 1.0; Z is oxygen or N—R₃; R₂ is —[CH₂]_(n)—; R₃ ishydrogen or —[CH₂]_(m)—CH₃; R₄ and R₅ are each, independently,—[CH₂]_(m)—CH₃; X is selected from the group consisting of Cl, Br, I andacetate; W is a bridging group or atom; m is an integer from 0 to 20; nis an integer from 1 to 20; and Y is selected from the group consistingof

wherein R₆, R₇ and R₈ are each, independently, selected from the groupconsisting of hydrogen, —[CH₂]_(q)—CH₃ and —CH(CH₃)₂; R₉ is —[CH₂]_(p);p is a number from 3 to 6 and q is a number from 0 to 3.

In one embodiment, R₁ is a C₁-C₆ alkyl group. In another embodiment, R₁is methyl, ethyl, propyl, butyl or isobutyl.

In one embodiment, a is from about 0.25 to about 0.50. In anotherembodiment, b is from about 0.50 to about 0.75. In another embodiment, cis from about 0.50 to about 0.75.

In one embodiment, Z is ammonia, trimethylammonia or triethylammonia.

W is a bridging group or atom. In one embodiment, W is a hydrocarbongroup, an inorganic group or inorganic atom. In one embodiment, W is aC₁-C₃₀ alkyl group, C₁-C₃₀ alkyl ether group, C₆-C₃₀ aromatic group,C₆-C₃₀ aromatic ether group or a siloxane. In another embodiment, W is aC₁-C₆ alkyl group, C₁-C₆ alkyl ether group, a C₆-C₁₀ aromatic group or aC₆-C₁₀ aromatic ether group. In another embodiment, W is methyl, ethyl,propyl, butyl, isobutyl, phenyl, 1,2-cyclohexanedicarboxylate, bisphenolA, diethylene glycol, resorcinol, cyclohexanedimethanol,poly(dimethylsiloxane), 2,6-tolylene diisocyanate, 1,3-butadiene ordicyclopentadiene.

In one embodiment, m is an integer from 0 to 10, including from 0 to 5.In another embodiment, n is an integer from 1 to 10, including from 1 to5.

In one embodiment, the ion exchange material may be anion exchange resinbeads or an anion exchange membrane.

In another embodiment, a method for making an ion exchange materialcomprises reacting a tertiary amine, an acid inhibitor and a polyepoxideto form a quaternary ammonium monomer and polymerizing the quaternaryammonium monomer in the presence of a catalyst.

An anion exchange membrane may be formed by any method known in the art.In one embodiment, the membrane is formed by reinforcing a fabric withthe anion exchange polymer. A liquid mixture of the reactants can beapplied to the fabric by casting the liquid monomer mixture onto thefabric or by soaking the fabric in the liquid mixture using individualpieces of fabric, multiple pieces of fabric arranged in stacks or withfabric from a roll in a continuous process. When heat is applied, thereaction between the reactants and polymerization will occur to form acrosslinked anion exchange membrane supported by a fabric.

In another embodiment, the membrane is formed by imbibing a porousplastic film, such as polyethylene, polypropylene or Teflon®, with theanion exchange polymer. A liquid mixture of the reactants can be appliedto the porous plastic film by casting the liquid monomer mixture ontothe porous plastic film or by soaking the porous plastic film in theliquid mixture. When heat is applied, the reaction between the reactantsand polymerization will occur to form a crosslinked anion exchangemembrane supported by a porous plastic film.

The anion exchange monomers can also be polymerized into a solid mass,processed and pulverized into small particles. The small particles canthen be blended in an extruder and heated with a melted plastic, such aspolyethylene or polypropylene. The plastic and ion exchange mixture canthen be extruded into thin sheets of ion exchange membranes.

Exchange resin beads may be produced by suspending the mixture of thereactants in a water immiscible organic media and heating to form ionexchange beads. When heat is applied, the reaction between the reactantsand polymerization will occur. Beads may also be produced by a vibratoryspray mechanism.

In order that those skilled in the art will be better able to practicethe present disclosure, the following examples are given by way ofillustration and not by way of limitation.

EXAMPLES Example 1

DMAPMA (30.6 g, 0.18 mole), hydrochloric acid (15.4 g, 0.16 mole),1,2,3-propanetriol glycidyl ether (GE100) (23.6 g, 0.09 mole) and 28.0 gof water were mixed and stirred for one hour. 1.4 g of a catalyst,2,2′-azobis(N,N′-dimethylene isobutyramidine) dihydrochloride suppliedby Wako Chemicals USA, Dallas, Tex. (VA044), was added and the mixturewas spread onto acrylic cloth between two Mylar sheets and sandwichedbetween glass plates. The resulting assembly was heated to 85° C. for 30minutes. The sandwich was separated and the resulting anion exchangemembrane was placed into water.

The following membrane properties were obtained:

Cap (meq/g)=2.67

Water content (%)=43.8

Resistivity (ohm-cm²)=11.1

Thickness (cm)=0.063

The anion exchange capacity was expressed as milligram-equivalents pergram of dry anion exchange resin in the nitrate form (i.e., notincluding fabric). The water content was expressed as percent by weightof the wet anion exchange resin in the nitrate form (i.e., not includingfabric). The areal resistance of a square centimeter of membrane in thechloride form was measured in 0.01N NaCl at 1000 Hz.

Example 2

DMAPMA (30.6 g, 0.18 mole), hydrochloric acid (15.4 g, 0.16 mole),1,2,3-propanetriol glycidyl ether (GE100) (23.6 g, 0.09 mole), N-Vinylcaprolactam (9.4 g, 0.068 mole) and 28.0 g of water were mixed andstirred for one hour. 1.4 g of a catalyst, 2,2′-azobis(N,N′-dimethyleneisobutyramidine) dihydrochloride supplied by Wako Chemicals USA, Dallas,Tex. (VA044), was added and the mixture was spread onto acrylic clothbetween two Mylar sheets and sandwiched between glass plates. Theresulting assembly was heated to 85° C. for 30 minutes. The sandwich wasseparated and the resulting anion exchange membrane was placed intowater.

The following membrane properties were obtained:

Cap (meq/g)=2.35

Water content (%)=42.9

Resistivity (ohm-cm²)=15.4

Thickness (cm)=0.067

The anion exchange capacity was expressed as milligram-equivalents pergram of dry anion exchange resin in the nitrate form (i.e., notincluding fabric). The water content was expressed as percent by weightof the wet anion exchange resin in the nitrate form (i.e., not includingfabric). The areal resistance of a square centimeter of membrane in thechloride form was measured in 0.01N NaCl at 1000 Hz.

While typical embodiments have been set forth for the purpose ofillustration, the foregoing descriptions should not be deemed to be alimitation on the scope herein. Accordingly, various modifications,adaptations and alternatives may occur to one skilled in the art withoutdeparting from the spirit and scope herein.

1. A method for making an anion exchange polymer comprising reacting atertiary amine, an acid inhibitor and a polyepoxide to form a quaternaryammonium monomer and polymerizing the quaternary ammonium monomer in thepresence of a catalyst, wherein the tertiary amine is an ethylenictertiary amine, and wherein the polyepoxide is a diglycidyl ether or atriglycidyl ether.
 2. The method acclaim 1 wherein the tertiary amine isselected from the group consisting of dimethylaminopropylmethacrylamide,dimethylaminopropylacrylamide, diethylaminopropylmethacrylamide,dimethylaminoethylmethacrylate and mixtures thereof.
 3. The method ofclaim 2 wherein the tertiary amine monomer isdimethylaminopropylmethacrylamide.
 4. The method of claim 1 wherein thepolyepoxide is selected from the group consisting of diethylene glycoldiglycidyl ether, diglycidyl 1,2-cyclohexanedicarboxylate,N,N-diglycidyl-4-glycidyloxyaniline, biisphenol A diglycidyl ether,brominated bisphenol A diglycidyl ether, bisphenol F diglycidyl ether,1,4-butanediol diglycidyl ether, 1,4-butanediyl diglycidyl ether,1,4-cyclohexanedimethanol diglycidyl ether, glycerol diglycidyl ether,resorcinol diglycidyl ether, bis[4-(glycidyloxy)phenyl]methane,bisphenol A propoxylate diglycidyl ether, dimer acid diglycidyl ester,ethylene diglycidyl ether, brominated neopentyl glycol diglycidyl ether,diglycidyl ether-terminated poly(dimethylsiloxane), poly(ethyleneglycol) diglycidyl ether, poly(propyleneglycol)diglycidyl ether,1,2,3-propanetriol glycidyl ether, 1,3-butanediol diglycidyl ether,tris(2,3-epoxypropyl)isocyanurate, trimethylolpropane triglycidyl ether,tris(4-hydroxyphenyl)methane triglycidyl ether 2,6-tolylenediisocyanate, tris(4-hydroxyphenyl)methane triglycidyl ether, glycerolpropoxylate triglycidyl ether and trimethylolethane triglycidyl ether.5. The method of claim 1 wherein the reaction is heated from about 40°C. to about 150° C. from about 1 minute to about 2 hours.
 6. The methodof claim 1 wherein the acid inhibitor is hydrochloric acid, methanesulfonic acid, sulfuric acid or phosphoric acid.
 7. The method of claim1 wherein the ratio of the moles of tertiary amine per equivalent moleof the polyepoxide is from about 0.3 to about 1.5.
 8. The method ofclaim 1 further comprising adding an ethylenic monomer.
 9. The method ofclaim 8 wherein the ethylenic monomer is selected from the groupconsisting of methacrylamine, N-methylmethacrylamide, N-vinylpyrrolidinone, N-vinyl caprolactam, methacrylamidopropyltrimethylammonium chloride and trimethylammoniumethyl methacrylatechloride.